System and method of transfer printing an organic semiconductor

ABSTRACT

The present invention provides a substrate having thereon a patterned small molecule organic semiconductor layer. The present invention also provides a method and a system for producing a substrate having thereon a patterned small molecule organic semiconductor layer. The substrate having thereon a patterned small molecule organic semiconductor layer is produced by exposing a donor substrate having thereon a small molecule organic semiconductor layer to energy to cause the thermal transfer of a small organic molecule onto an acceptor substrate.

This application is related to commonly-owned U.S. Application entitled“The Use of an Energy Source to Convert Precursors into PatternedSemiconductors,” Ser. No. 10/314,607, filed herewith on the same day,Dec. 9, 2002, cross-referenced and incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to substrates having thereon a patternedsmall molecule organic semiconductor layer. The invention also relatesto a method and a system for the production of such substrates havingpatterned small molecule organic semiconductor layers thereon. Thepatterned small molecule organic semiconductor layer is formed by thethermal transfer of a small molecule organic semiconductor or itsprecursor from a donor substrate to an acceptor substrate. Moreparticularly the present invention relates to a substrate having thereona patterned pentacene semiconductor layer.

2. Description of the Prior Art

The concept of transfer printing of inks and various metals is one thathas been known for some time. The general idea involves a substanceadhering or affixed to a first surface to be transferred to a secondsurface with or without direct physical contact between the twosurfaces. This type of transfer is well known in non-impact printing oftext and also used for transfer of various metals from a first surfaceto a second surface, usually by way of local pulsed heating of the donorsurface. The present invention utilizes preferably a flexible substrateor ribbon or other donor substrates (not necessarily flexible) whichcontain a small molecule organic semiconducting compound or itsprecursor that can be locally heated resulting in a transfer, likely bysublimation, of the small molecule organic semiconducting or precursormaterial from the donor surface resulting in adhesion of the organicsemiconductor onto a second or acceptor surface. The transfer ofmaterial can be used to define a localized pattern on the acceptorsubstrate, for example a material that can be used to create a componentof a semiconducting device. When the heating method utilizes a focusedlaser beam, either incident on the semiconducting material or precursorof a small molecule semiconductor such as pentacene, a very narrow andwell defined transfer can be achieved to define a part of asemiconducting device, for example the channel of a field effecttransistor (FET) or various other semiconducting devices.

Non-impact transfer printing has been used for a variety of applicationsfor a number of years. This form of printing can be divided into twocategories; first, one in which there is no contact between the firstsurface of the donor substrate from which material is transferred andthe first surface receiving the material; and second, one in which thetwo surfaces are in contact but in which there is no impact to impartthe material from the first surface of the donor to the first surface ofthe acceptor. Examples of these types of material transfers are wellknown in the literature. The transfer of material from a donor surfaceto an acceptor surface where the acceptor surface may have beenpreviously chemically treated to cause a chemical reaction with thetransferred material has been described extensively. For example, inkjet type printers for printing semiconductors and other components ofsemiconductor devices have been known for some time and are describedagain most recently in U.S. 2002/0053320 A1.

U.S. Pat. No. 6,344,660 describes impact printing which involves contactbetween a first and second substrate, wherein the first substratecarries ink or some metal that is to be transferred to the secondsubstrate by local heating, stamping, or spin coating.

When melting is used to transfer material, the source of heat may be afocused laser beam incident on the donor substrate, with a portion ofthe laser or other energy beam absorbed by the first surface which maybe a ribbon. Alternatively, the ribbon may contain an electricallyconducting stripe which can be used for localized printing due to thecontact of a high resistance element between the contact point on theribbon and the electrically conducting stripe in which case this form ofheating takes the place of the laser to cause the melting and transferof the material. Print heads that heat the ribbon in one or more placessimultaneously are also well known to achieve thermal transfer.

However, there is no prior art known to us in which semiconductingmaterials are transferred to a second substrate in a crystalline form.In general, to transfer a semiconductor from one surface to a secondsurface has been achieved by the melting of the material which then istransferred by vaporization from the molten state to a second substrateresulting in an amorphous film. In general, this technique has beenwidely used in the processing of electroluminescent devices but withoutthe use of a precursor that includes a small organic semiconductingmolecule.

It has recently been discovered that small organic semiconductingmolecules, such as pentacene, can be thermally transferred from certainsubstrates (donor substrate) to a second substrate (acceptor substrate)using localized heating. This results in a type of small moleculedeposition using energy to provide the thermal energy for the transfer.This type of transfer can be made in a partial vacuum. In more recentexperiments it has been found that intimate contact between the donorsubstrate (containing a pre-deposited small molecule organicsemiconductor layer of either the small organic molecule itself or aprecursor to that small molecule) and the acceptor substrate yieldextremely fine thermally transferred patterns of the small organicmolecule onto the acceptor substrate using a focused laser beam. It hasbeen found that the transfer can take place in an ambient atmospheresince the contact between donor and acceptor are sufficiently close toone another that very little, if any of the atmosphere is trappedbetween the contacting substrates nor can the ambient air enter betweenthe acceptor and donor. This type of intimate contact also precludes thepossibility of any substantial contamination of the transferred organic(e. g. pentacene) from the outside ambient.

Thin-film transistors and other electronic devices using organicsemiconductors, such as pentacene, are emerging as alternatives toestablished methods using amorphous silicon (α-Si:H) as thesemiconductor.

A variety of organic compounds have been proposed and tested assemiconducting materials for TFT devices. For example, among thep-channel (hole transport) materials that have been characterized arethiophene oligomers proposed as organic semiconductor material for TFTin Garnier, F., et al., “Structural basis for high carrier mobility inconjugated oligomers” Synth. Meth., Vol. 45, p. 163 (1991), andphthalocyanines described in Bao, Z., et al., “Organic Filed-effecttransistors with high mobility based on copper phthalocyanine” Appl.Phys. Lett., Vol. 69, p. 3066 (1996). Pentacene, which is a member ofpoly(acene) compounds has been proposed as an organic semiconductormaterial in Lin et al. IEEE 54th Annual Device Research Conference,1996, pages 2136-2139, and Dimitrakopoulos et al., J. Appl. Phys., 80(4), 1996, pages 2501-2507.

Some soluble organic compounds have also been characterized as organicsemiconducting materials. For example poly(3-alkylthiophene) describedin Bao, Z., et al., “Soluble and Processable regioregularpoly(3-hexylthiophene) for thin film field-effect transistorsapplication with high mobility” Appl. Phys. Lett., Vol. 69, page 4108(1996).

An attractive material would have a high carrier mobility which is closeto that of amorphous silicon (0.1-1 cm².V⁻¹.s⁻¹), with a very highon/off ratio (>10⁵). For an organic material to replace amorphoussilicon would have not only the electrical properties cited above butalso should be processable from solution so that it could becomecommercially attractive.

Among the organic compounds which have been studied as semiconductors,only regioregular poly(3-hexylthiophene) is readily soluble in organicsolvents and thin films of this compound have been processed fromsolution for construction of TFTs. The drawback for this compound isthat it has relatively low (5×10⁻² cm².V⁻¹.s.⁻¹) carrier mobility andeven much less satisfactory on/off ratio of less than 100. In addition,because thin films of this polymer are not stable in air and itsfield-effect characteristics deteriorate on exposure to air, itsapplication as semiconductor becomes less desirable.

The best performance as a semiconductor among organic materials to datehas been achieved by thin films of pentacene deposited under high vacuumand temperature as reported by Dimitrakopoulos et al., in U.S. Pat. Nos.5,946,511; 5,981,970 and 6,207,472 and other publications by Brown etal., J. Appl. Phys. 80(4), 1996, pages 2136-2139 and Dimitrakopoulos etal., J. Appl. Phys. 80(4), pages 2501-2507.

Recently, thin-film transistors on plastic substrates using evaporatedfilms of pentacene as the p-channel carrier with mobility of 1.7cm².V⁻¹.s.⁻¹ and an on/off ratio of 10⁸ have been reported by Jakson etal., in Solid State Technology, Vol. 43 (3), 2000, pages 63-77.

Thin films of pentacene are very stable in air and even moderatetemperatures and as far as performance is concerned, pentacene isprobably the most attractive organic material to date to replaceamorphous silicon.

The drawback of pentacene is that it is insoluble in common organicsolvents and can only be deposited as a thin film by expensive highvacuum and temperature techniques.

There has been very little effort for the synthesis of soluble pentacenederivatives and the only example of soluble pentacene is by Muellen, K.et al., “A soluble pentacene precursor: Synthesis, solid-stateconversion into pentacene and application in a field-effect transistor,”Adv. Mat. 11(6), p. 480 (1999), in which a precursor of pentacene issynthesized by a tedious multi-step synthetic approach. The derivative,which is soluble in organic compounds and can be processed fromsolution, is converted back to pentacene by heating at moderate to hightemperatures (140-200° C.).

The drawback for using this compound as a pentacene precursor is thatdue to the multi-step synthesis (more than 9 steps), its preparation,especially in large scale is impractical. In addition, its conversion topentacene occurs at a relatively high temperature which prevents the useof most plastics as substrates.

Commonly owned and copending application entitled “Hetero Diels-AlderAdducts of Pentacene as Soluble Precursors of Pentacene,” Ser. No.10/300,645, Filed on Nov. 20, 2002, IBM ref: YOR920020160US1, contentsof which are incorporated herein by reference, describes a speciallyprepared pentacene precursor that can be spun, dipped, or sprayed onto asubstrate from which a small molecule organic semiconductor can resultfrom simple thermal processing of the precursor. The precursor, afterapplication to a substrate, is then allowed to dry. Upon heating thesubstrate (upon which the dried precursor film resides) on a hot plateat temperatures of 200° C. or less for several minutes or less theprecursor has been shown to transform into a pure small molecule organicsemiconductor, such as pentacene. Commonly owned and copendingapplication entitled “Thin Film Transistors Using Solution ProcessedPentacene Precursor as Organic Semiconductor,” Ser. No. 10/300,630,filed on Nov. 20, 2002, IBM ref: YOR 920020161US1, contents of which areincorporated herein by reference, describes the application of asolution processed polycyclic aromatic compound precursors as an organicsemiconducting material in thin film transistors.

The present invention describes a method and a system for producing asubstrate having thereon a patterned small molecule organicsemiconductor layer, and the patterned substrate itself, wherein thepatterned small molecule organic semiconductor layer is produced fromthe thermal transfer of the small organic molecule from a donor. Thesmall organic molecule feature distinguishes the present invention fromthose that have transferred polymer or polymer semiconductors from onesurface to a second surface in several ways. There is interest in theuse of small molecule organic semiconductors in manufacturing items suchas light emitting diodes, photodiodes, and field effect transistors(FET's). The present invention provides a cost savings from the usualmethod of semiconductor device production which normally employsexpensive lithographic processes here circumvented by the presentinvention.

Organic semiconductors are generally cheaper to produce for theseapplications and are also easier to process as they can be deposited atlow temperatures. In addition, this widens the choice of possiblesubstrates including flexible ones that are available in large areassuch as MYLAR™ and KAPTON™.

The prior art does not disclose the transfer of small molecules using asimple process of thermal transfer to form patterned layers of the smallorganic molecule semiconductor material in crystalline form on asubstrate.

Accordingly, it is an object of the present invention to provide amethod and a system for producing a substrate having thereon a patternedsmall molecule organic semiconductor layer produced by exposing a donorsubstrate having thereon a small molecule organic semiconductor layer toenergy thus causing the thermal transfer of the small organic moleculeonto an acceptor substrate to form the patterned small molecule organicsemiconductor layer thereon. The principal application addresses themanufacture of organic field effect transistors (FET's) and organiclight emitting diodes on a large scale that that is essentiallyautomated. However, the apparatus and method are not limited topentacene and can have applications to organic compounds other thanpentacene, especially small organic semiconductor molecules.

SUMMARY OF THE INVENTION

The present invention provides a substrate having thereon a patternedsmall molecule organic semiconductor layer having a small organicmolecule thermally transferred by exposing a donor substrate havingthereon a small molecule organic semiconductor layer to energy.

The present invention further provides a method of preparing a substratehaving thereon a patterned small molecule organic semiconductor layer,involving the exposure of a donor substrate having thereon a smallmolecule organic semiconductor layer to energy produced from an energysource to cause the thermal transfer of a small organic molecule onto anacceptor substrate to produce a substrate having thereon the patternedsmall molecule organic semiconductor layer.

The present invention also provides a system for producing a substratehaving thereon a patterned small molecule organic semiconductor layer.The system has a donor substrate having thereon a small molecule organicsemiconductor layer; an acceptor substrate positioned to receive saidpatterned small molecule organic semiconductor layer upon exposing thedonor substrate to energy; and an energy source to produce said energyto cause the thermal transfer of a small organic molecule onto theacceptor substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a substrate having thereon a patterned small moleculeorganic semiconductor layer.

FIG. 2 shows a system incorporating an acceptor substrate, a donorsubstrate of energy absorbing material having thereon a small moleculeorganic semiconductor layer, and energy produced from an energy sourceyielding a maskless pattern on the acceptor substrate.

FIG. 3 shows a system incorporating an acceptor substrate, a donorsubstrate of energy transparent material having thereon a small moleculeorganic semiconductor layer with an energy absorbing film interposedbetween the two, and energy produced from an energy source.

FIG. 4 shows a representative system of this invention with means formoving the donor and acceptor substrates relative to each other and theenergy.

FIG. 5 shows a representative system of this invention with means formoving the energy source relative to the acceptor and donor substrates.

FIG. 6(a) shows an acceptor substrate with means for movement and anenergy transparent donor substrate with means for movement, a smallmolecule organic semiconductor layer, an energy absorbing film, and asource of energy with means for movement wherein the energy floodilluminates the donor substrate. The energy absorbing film absorbs theenergy thereby heating the small molecule organic semiconductor layer,thus causing the thermal transfer of the small organic molecule which ispatterned onto the acceptor substrate by the insertion of a mask betweenthe donor and acceptor substrates.

FIG. 6(b) shows a top view of a mask with an “H” pattern opening and anacceptor substrate behind the mask.

FIG. 7 shows a representative system and method of the invention withthe donor substrate being a rotatable disk with means to rotate aroundits axis and means to move the rotatable disk relative to the energysource and the acceptor substrate. The energy source and acceptorsubstrate also have means for movement.

FIG. 8 shows a representative system and method of the invention wherethe acceptor substrate has a component of an electronic structurethereon.

FIG. 9 shows an acceptor substrate with the elements of a field effecttransistor (FET) thereon and a patterned small molecule organicsemiconductor layer deposited as the channel of the FET without the useof a mask.

FIG. 10 shows a reel-to-reel apparatus where the donor substrate is aribbon that is wound from one reel to the other while energy causes thethermal transfer of small molecule from the donor substrate to theacceptor substrate.

FIG. 11(a) shows a side view of a hollow cylindrical roller where theenergy source is at a point along the axis. The hollow cylindricalroller is here constructed of an energy transparent material and hasthereon a small molecule organic semiconductor layer with an energyabsorbing film therebetween. The energy from the energy source isincident on the inner surface of the hollow cylindrical roller in thedirection of the acceptor substrate and causes the thermal transfer ofsmall molecule from the hollow cylindrical roller to the acceptorsubstrate. This figure illustrates the optional means for exertingpressure on the hollow cylindrical roller to place it in intimatecontact with the acceptor substrate.

FIG. 11(b) shows a cross sectional view of a hollow cylindrical rollerwhere the energy source is at a point along the axis with the ability tomove along the axis and to have the axis moved relative to the hollowcylindrical roller.

FIG. 12 shows an energy transparent donor substrate with an energyabsorbing film and a small molecule organic semiconductor layer passingin intimate contact with an acceptor substrate between a hollowcylindrical roller with an energy source at a point within and a secondroller. Each roller depicted has optional means for exerting pressure.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a substrate having thereon a patternedsmall molecule organic semiconductor layer having a small organicmolecule thermally transferred by exposing a donor substrate havingthereon a small molecule organic semiconductor layer to energy.

The present invention further provides a method of preparing a substratehaving thereon a patterned small molecule organic semiconductor layer,involving the exposure of a donor substrate having thereon a smallmolecule organic semiconductor layer to energy produced from an energysource to cause the thermal transfer of a small organic molecule onto anacceptor substrate to produce a substrate having thereon the patternedsmall molecule organic semiconductor layer.

The present invention also provides system for producing a substratehaving thereon a patterned small molecule organic semiconductor layer.The system has a donor substrate having thereon a small molecule organicsemiconductor layer; an acceptor substrate positioned to receive saidpatterned small molecule organic semiconductor layer upon exposing thedonor substrate to energy; and an energy source to produce said energyto cause the thermal transfer of a small organic molecule onto theacceptor substrate.

The present invention provides a substrate having thereon a patternedsmall molecule organic semiconductor layer. FIG. 1 shows a crosssectional view of a substrate 100 with a patterned small moleculeorganic semiconductor layer 105. The substrate with the patterned smallmolecule organic semiconductor layer is prepared by exposing a donorsubstrate which has a small molecule organic semiconductor layer on itto energy produced from an energy source. The exposure causes thermaltransfer, such as sublimation and deposition, of a small organicmolecule from the small molecule organic semiconductor layer on thedonor substrate and the deposition of that small molecule onto anacceptor substrate

The donor substrate can be made of an energy absorbing or an energytransparent material, or a combination of absorbing and transparentmaterials. The donor substrate may also contain areas not directlyinvolved with the thermal transfer process that are neither transparentnor absorptive to energy.

When the donor substrate is made of an energy absorbing material, thesmall molecule organic semiconductor layer is directly on the donorsubstrate. In this case the energy is absorbed by the energy absorbingmaterial and heat is produced. It is this heat that causes the thermaltransfer of the small organic molecule onto the acceptor substrate.

FIG. 2 shows a cross sectional view of a simple system of the presentinvention and is illustrative of the method involving an energyabsorbing donor substrate. A small molecule organic semiconductor layer200 has been pre-deposited on an energy absorbing donor substrate 205.The small molecule organic semiconductor layer 200 can also be producedby the at least partial conversion of a precursor of the small organicmolecule during the step of exposing the donor substrate to energy. Thispreferred embodiment of preparing the small molecule organicsemiconductor layer from a precursor is discussed in further detailbelow and can be employed in all embodiments of the current invention.In FIG. 2 energy 215 from energy source 210 is incident on the surfaceof the energy absorbing donor substrate 205 opposite the small moleculeorganic semiconductor layer 200. This is a preferred direction fromwhich to direct the energy, however, a person of ordinary skill in theart would be capable of configuring the direction in a variety of ways.Energy 215 is absorbed by the energy absorbing donor substrate 205. Heatfrom the absorption of energy 215 is rapidly transferred to the smallmolecule organic semiconductor layer 200 causing the thermal transfer ofthe small organic molecule from the surface of the donor substrate 205to the acceptor substrate 100 depositing a patterned small moleculeorganic semiconductor layer 225 corresponding in area to the heatedregion of the small molecule organic semiconductor layer 200 on thedonor substrate 205. Depending on the relative positioning of the energy215, donor substrate 205, and the acceptor substrate 100 a wide varietyof patterns of the small organic molecule can be formed on the acceptorsubstrate 100. FIG. 2 shows a single region of deposition indicated bythe patterned small molecule organic semiconductor layer 225 whichcorresponds to the diameter of the energy 215.

When the donor substrate is made of an energy transparent material, anenergy absorbing film, such as a thin film, can be interposed betweenthe donor substrate and the small molecule organic semiconductor layer.In this case the energy passes through the energy transparent materialof the donor substrate and is absorbed by the energy absorbing film,thus producing heat. It is this heat that causes the thermal transfer ofthe small organic molecule onto the acceptor substrate. Non-limitingexamples of materials for the energy absorbing film include platinum,titanium, chromium, and organics such as KAPTON™.

FIG. 3 shows a cross sectional view of another simple system of thepresent invention and is illustrative of the method involving an energytransparent donor substrate. A small molecule organic semiconductorlayer 200 has been pre-deposited on an energy transparent donorsubstrate 300 with an energy absorbing film 305 interposed between 200and 300. Energy 215 from energy source 210 is incident on the surface ofthe energy transparent donor substrate 300 opposite the small moleculeorganic semiconductor layer 200. Energy 215 penetrates the energytransparent substrate 300 and is absorbed by the energy absorbing film305. Heat from the absorption of energy 215 is rapidly transferred tothe small molecule organic semiconductor layer 200 causing the thermaltransfer of the small organic molecule from the surface of the donorsubstrate 300 to the acceptor substrate 100 depositing a patterned smallmolecule organic semiconductor layer 225 corresponding in area to theheated region of the small molecule organic semiconductor layer 200 onthe donor substrate 300. Depending on the relative positioning of theenergy 215, donor substrate 300, and the acceptor substrate 100 a widevariety of patterns of the small organic molecule can be formed on theacceptor substrate 100. FIG. 3 shows a single region of depositionindicated by the patterned small molecule organic semiconductor layer225 which corresponds to the diameter of the energy 215.

The donor substrate can be made of any suitable material. Non-limitingexamples of materials that are suitable for use as the donor substrateinclude glass, silicon, polyimide, and polymethyl methacrylate (PMMA).

The acceptor substrate can be made of any suitable material.Non-limiting examples of materials that are suitable for use as theacceptor substrate include glass, silicon, polyimide, and polymethylmethacrylate (PMMA).

The energy absorbing film can be of a thickness of from about 100 toabout 20,000 Angstroms. The energy absorbing film can be applied to thedonor substrate by any well known process. Non-limiting examples ofapplication methods include sputtering, evaporating, spraying, dipping,spinning, or combinations thereof.

The small molecule organic semiconductor layer can also be applied tothe donor substrate by any well known process. Non-limiting examples ofapplication methods include sputtering, evaporating, spraying, dipping,spinning, or combinations thereof.

As mentioned previously, the small molecule organic semiconductor layeron the donor substrate can be a film, such as a thin film, of the smallorganic molecule itself or it can be formed during the step of exposingthe donor substrate to energy from a precursor of the small organicmolecule.

In the context of the present invention, the term small organic moleculerefers to a non-polymeric organic semiconducting material which is asolid. Examples of such small organic molecules include polycyclicaromatic compounds, such as oligothiophene, perylene,benzo[ghi]perylene, coronene and polyacene.

In the case that the small molecule organic semiconductor layer isformed from a precursor, the chemical structure of the precursor is suchthat only the small organic molecule becomes transferred by thermaltransfer upon application of energy. The remaining chemical constituentsof the precursor become volatized and do not deposit on the acceptorsubstrate.

The small molecule organic semiconductor layer can be made up of thesmall organic molecule that is to be thermally transferred to theacceptor substrate. The small organic molecule can be a polycyclicaromatic compound. Non-limiting examples of polycyclic aromaticcompounds that are useful in the present invention includeoligothiophene, perylene, benzo[ghi]perylene, coronene, and polyacene.Preferred polyacenes include those represented by the formula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, a group wherein R³ and R⁴ together form one or more fused benzorings and a group wherein R⁵ and R⁶ together form one or more fusedbenzo rings; wherein n is at least 1. Pentacene, which is an example ofa polyacene, is a preferred, but non-limiting, example of the smallorganic molecules that can be utilized in this invention.

When the small molecule organic semiconductor layer is produced from aprecursor of the small organic molecule, the precursor can be, forexample, a precursor to a polycyclic aromatic compound; Diels-Alderadduct of a polycyclic aromatic compound with a dienophile, wherein thepolycyclic aromatic compound is selected from: oligothiophene, perylene,benzo[ghi]perylene, coronene and polyacene; and wherein the dienophileis represented by the formula:R¹—X═Y—R²

wherein each X and Y can independently be N or CR⁷;

wherein R¹—X═ can be O, S, SO and SO₂; and

wherein each R¹, R² and R⁷ can independently be hydrogen, alkyl of 1-12carbon atoms, aryl, substituted aryl, aralkyl, alkoxycarbonyl,aryloxycarbonyl, acyl and a group R, wherein R can be hydrogen, alkyl of1-12 carbon atoms, alkoxy, acyl, aryl, aralkyl, chloroalkyl, fluoroalkyland substituted aryl having a substituent selected from: —F, —Cl, —Br,—NO₂, —CO₂R, —PO₃H, —SO₃H, trialkylsilyl and acyl; wherein the acyl isrepresented by the formula: R⁸CO— wherein R⁸ can be hydrogen, alkyl of1-12 carbon atoms, aryl, substituted aryl, aralkyl and fluoroalkyl;

with the proviso that at least one of X and Y is a hetero atom selectedfrom: N, O and S.

A preferred Diels-Alder adduct of a polycyclic aromatic compound with adienophile is represented by the formula:

wherein each X and Y is independently selected from: N and CR⁷;

wherein R¹—X═ can be O, S, SO and SO₂; and

wherein each R¹, R² and R⁷ is independently selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, aralkyl,alkoxycarbonyl, aryloxycarbonyl, acyl and a group R, wherein R can behydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl, aryl, aralkyl,chloroalkyl, fluoroalkyl and substituted aryl having a substituentselected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H, —SO₃H, trialkylsilyland acyl; wherein the acyl is represented by the formula: R⁸CO— whereinR⁸ can be hydrogen, alkyl of 1-12 carbon atoms, aryl, substituted aryl,aralkyl and fluoroalkyl;

with the proviso that at least one of X and Y is a hetero atom selectedfrom: N, O and S

The Diels-Alder adduct of a polycyclic aromatic compound with adienophile can be prepared by a process comprising the step ofcontacting:

(a) a polycyclic aromatic compound selected from: oligothiophene,perylene, benzo[ghi]perylene, coronene and a compound represented by theformula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, a group wherein R³and R⁴ together form one or more fused benzo rings and a group whereinR⁵ and R⁶ together form one or more fused benzo rings, wherein n is atleast 1; and

(b) dienophile represented by the formula:

 R¹—X═Y—R²

wherein each X and Y is independently selected from: N and CR⁷; whereinR¹—X═ can be O, S, SO and SO₂; wherein each R¹, R² and R⁷ isindependently selected from: hydrogen, alkyl of 1-12 carbon atoms, aryl,substituted aryl, aralkyl, alkoxycarbonyl, aryloxycarbonyl, acyl and agroup R, wherein R can be hydrogen, alkyl of 1-12 carbon atoms, alkoxy,acyl, aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted arylhaving a substituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H,—SO₃H, trialkylsilyl and acyl; wherein the acyl is represented by theformula: R⁸CO— wherein R⁸ can be hydrogen, alkyl of 1-12 carbon atoms,aryl, substituted aryl, aralkyl and fluoroalkyl; with the proviso thatat least one of X and Y is a hetero atom selected from: N, O and S;

wherein the contacting is carried out under reaction conditionssufficient to produce the Diels-Alder adduct.

A film, such as a thin film, of a Diels-Alder adduct of a polycyclicaromatic compound with a dienophile can be prepared by a methodcomprising the steps of:

(a) applying onto a substrate a solution of a Diels-Alder adduct of apolycyclic aromatic compound with a dienophile in a suitable solvent,wherein the polycyclic aromatic compound is selected from:oligothiophene, perylene, benzo[ghi]perylene, coronene and a compoundrepresented by the formula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, a group wherein R³and R⁴ together form one or more fused benzo rings and a group whereinR⁵ and R⁶ together form one or more fused benzo rings, wherein n is atleast 1; and

wherein the dienophile is represented by the formula:R¹—X═Y—R²

wherein each X and Y is independently selected from: N and CR⁷; whereinR¹—X═ can be O, S, SO and SO₂; and wherein each R¹, R² and R⁷ isindependently selected from: hydrogen, alkyl of 1-12 carbon atoms, aryl,substituted aryl, aralkyl, alkoxycarbonyl, aryloxycarbonyl, acyl and agroup R, wherein R can be hydrogen, alkyl of 1-12 carbon atoms, alkoxy,acyl, aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted arylhaving a substituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H,—SO₃H, trialkylsilyl and acyl; wherein the acyl is represented by theformula: R⁸CO— wherein R⁸ can be hydrogen, alkyl of 1-12 carbon atoms,aryl, substituted aryl, aralkyl and fluoroalkyl; with the proviso thatat least one of X and Y is a hetero atom selected from: N, O and S; and

(b) evaporating the solvent to produce the film of the Diels-Alderadduct of the polycyclic aromatic compound with the dienophile.

A film, such as a thin film, of a polycyclic aromatic compound can beprepared by a method comprising the steps of:

(a) applying onto a substrate a solution of a Diels-Alder adduct of apolycyclic aromatic compound with a dienophile in a suitable solvent,wherein the polycyclic aromatic compound is selected from:oligothiophene, perylene, benzo[ghi]perylene, coronene and a compoundrepresented by the formula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, a group wherein R³and R⁴ together form one or more fused benzo rings and a group whereinR⁵ and R⁶ together form one or more fused benzo rings, wherein n is atleast 1; and wherein the dienophile is represented by the formula:R¹—X═Y—R²

wherein each X and Y is independently selected from: N and CR⁷; whereinR¹—X═ can be O, S, SO and SO₂; and wherein each R¹, R² and R⁷ isindependently selected from: hydrogen, alkyl of 1-12 carbon atoms, aryl,substituted aryl, aralkyl, alkoxycarbonyl, aryloxycarbonyl, acyl and agroup R, wherein R can be hydrogen, alkyl of 1-12 carbon atoms, alkoxy,acyl, aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted arylhaving a substituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H,—SO₃H, trialkylsilyl and acyl; wherein the acyl is represented by theformula: R⁸CO— wherein R⁸ can be hydrogen, alkyl of 1-12 carbon atoms,aryl, substituted aryl, aralkyl and fluoroalkyl; with the proviso thatat least one of X and Y is a hetero atom selected from: N, O and S;

(b) evaporating the solvent to produce the film of the Diels-Alderadduct of the polycyclic aromatic compound with the dienophile; and

(c) heating the film of the Diels-Alder adduct at a temperature and fora period of time sufficient to convert the Diels-Alder adduct back tothe polycyclic aromatic compound.

Other fused aromatic compounds like oligothiophene, perylene (III),benzo[ghi]perylene (IV), coronene (V) and other fused aromatic compoundscapable of forming Diels-Alder adducts can also be used to preparesoluble precursors of these sparingly soluble compounds.

wherein n is equal or greater than 1, and preferably from 1 to 5; andwherein R¹ and R² are independently selected from the group consistingof hydrogen, alkyl of 1-12 carbon atoms, acyl, alkylphosphonate,hydroxyalkyl, mercaptoalkyl, thiol, carboxylic acid, carboxylic acidester, trialkoxysilane, amino, alkylamino, dialkylamino and aminoalkane.

A most preferred polycyclic aromatic compound is pentacene. Pentacene, asmall molecule organic semiconductor is particularly useful in makingorganic field effect transistors (FET's), as well as organic lightemitting diodes. Such organic semiconductors are particularly attractiveas they require relatively low temperature processing, the materials arerelatively inexpensive and they can be deposited on flexible substrates.These qualities are all advantageous compared to conventional silicontechnology as it is employed today in manufacturing of these devices.

An example of such an adduct wherein the polycyclic aromatic compound ispentacene and the dienophile is a thioxocarboxylate is represented bythe formula:

The above Diels-Alder adduct in which the sulfur atom is oxidized to thecorresponding sulfoxide is represented by the formula:

wherein R is selected from: hydrogen, alkyl of 1-12 carbon atoms,alkoxy, acyl, aryl, aralkyl, chloroalkyl, fluoroalkyl and substitutedaryl having a substituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R,—PO₃H, —SO₃H, trialkylsilyl and acyl; wherein said acyl is representedby the formula: R⁸ CO— wherein R⁸ is selected from: hydrogen, alkyl of1-12 carbon atoms, aryl, substituted aryl, aralkyl and fluoroalkyl;

Another example is the Diels-Alder reaction of thioxomalonate withpentacene to form an adduct with one carbon-sulfur bond as depicted inthe following scheme. Diethyl thioxomalonate is prepared in situ fromthe reaction of diethyl oxomalonate and phosphorous pentasulfide andreacted with pentacene in the presence of a catalyst or by heating inpyridine.

wherein each R is independently selected from: hydrogen, alkyl of 1-12carbon atoms, alkoxy, acyl, aryl, aralkyl, chloroalkyl, fluoroalkyl andsubstituted aryl having a substituent selected from: —F, —Cl, —Br, —NO₂,—CO₂R, —PO₃H, —SO₃H, trialkylsilyl and acyl; wherein said acyl isrepresented by the formula: R⁸CO— wherein R⁸ is selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, aralkyl andfluoroalkyl;

At temperatures higher than 150° C., the thioxomalonate adduct, which isisolated by column chromatography as a white crystalline compound,undergoes a retro Diels-Alder reaction to pentacene. However, if thesulfide is oxidized to corresponding S-oxide, then the adduct can beconverted back to pentacene at temperature as low as 150° C.

Both the sulfide and S-oxide adduct are highly soluble in common organicsolvents and can be processed from solution to form films on substrates.

Another class of adducts of pentacene is Diels-Alder reaction productsof pentacene and dialkyl or diaralkylazodicarboxylates. These compoundsare by themselves thermally labile and decompose above 100° C.Therefore, any Diels-Alder reaction of these compounds with pentacenehas to be carried out low to moderate temperature.

The Diels-Alder adduct where the dienophile is an azodicarboxylate ofthe formula RO—CO—N═N—COOR is shown below:

R can be alkyl of 1-12 carbon atoms, aryl, aralkyl, chloroalkyl,fluoroalkyl and substituted aryl having a substituent selected from: —F,—Cl, —Br, —NO₂, —CO₂R, trialkylsilyl and acyl; wherein the acyl isrepresented by the formula: R⁸CO— wherein R⁸ can be hydrogen, alkyl of1-12 carbon atoms, aryl, substituted aryl, aralkyl, chloroalkyl andfluoroalkyl.

Preferably, R is benzyl, alkyl of one to five carbon atoms, partially orfully chlorinated alkyl of one to four carbon atoms and partially orfully fluorinated alkyl of one to four carbon atoms.

The above Diels-Alder can be hydrolyzed to form a cyclic diaminecompound represented by the formula:

and the diamine can be oxidized to give an azo compound represented bythe formula:

Employing a Lewis acid catalyst, such as, titanium tetrachloridefacilitates the Diels Alder reaction so it can be carried out attemperature below −40° C. Alternatively, less active catalysts likesilver tetrafluoroborate or methyl rhenium trioxide can be used to runthe reaction above room temperature by refluxing the mixture ofpentacene, diazodicarboxylate and the catalyst in a low boiling solventlike THF or chloroform.

These diaza adducts of pentacene are stable to high temperatures and assuch are not good candidates as pentacene precursors because films ofthese compounds have to be heated above 280° C. to convert to pentacene.For example, the adduct of diethyl diazodicarboxylate (R=ethyl) has amelting point of 257° C. and is stable up to 300° C. But when thecarboxylate groups are hydrolyzed to the corresponding acid, whichautomatically undergo decarboxylation to form the cyclic diamine, oroxidized form of the latter to diazo derivative, then the adduct becomeshighly unstable and can be converted back to pentacene at moderatetemperatures (50-100° C.). Thus, an important step in this process isthe removal of the carboxylate protecting group at low temperatures soas to be able to isolate the amine or diazo compounds.

The adducts of pentacene with a variety of dialkyl azodicarboxylate wereprepared. It was found that bis-trichloroethyl carboxylates(R=CCl₃—CH₂—) can easily be removed at room temperature in THF bytreatment with zinc powder to give the corresponding diamine.

In yet another example of Diels-Alder reaction of pentacene with heterodienophiles, N-Sulfinyl acetamide (R=CH₃CO—) and N-sulfinyl benzylcarbamate (R=C₆H₅CH₂OCO—) were prepared and reacted with pentacene inthe presence of methyl rhenium trioxide as Lewis acid catalyst. In bothcases, high yields of the adduct were obtained and the compounds foundto be highly soluble in many organic solvents.

Films of these compounds were cast from solution and then heated at120-140° C. to transform the compounds back to pentacene is confirmed byits UV/VIS spectra and thermogravimetric analysis TGA and IR spectrum.Although the onset of the retro Diels-Alder reaction temperature forbulk, as evident from TGA, is about 140° C., films of these compoundscan be converted back to pentacene at even lower temperatures of110-120° C.

In still another example of Diels-Alder reaction of pentacene withhetero dienophiles, a Diels-Alder adduct wherein the dienophile is anN-sulfinyl amide compound is represented by the formula:RCO—N═S═O

and the adduct is represented by the formula:

wherein R can be hydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl,aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted aryl having asubstituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H, —SO₃H,trialkylsilyl and acyl; wherein the acyl is represented by the formula:R⁸CO— wherein R⁸ can be hydrogen, alkyl of 1-12 carbon atoms, aryl,substituted aryl, aralkyl and fluoroalkyl.

The above Diels-Alder adduct can be hydrolyzed to form a compoundrepresented by the formula:

Although only two examples of N-sulfinyl amides are shown here,N-sulfinyl derivatives are equally attractive candidates for thepreparation of soluble pentacene adducts.

For example, N-sulfinyl derivative of fluoroalkylamide liketrifluoracetamide (R=CF₃—CO—) or higher alkyl amides(R=C_(n)H_(2n+1)—CO—, where n=1-10) can be used instead of sulfinylacetamide. N-Sulfinyl derivatives of aromatic amines (R=aryl) where R—issimply a phenyl group or substituted (nitro, keto, halo, alkyl,fluoroalkyl etc) are known to undergo Diels-Alder reactions and can beused to prepare soluble adducts with pentacene.

In another example of the Diels-Alder reaction of pentacene with ahetero dienophile, a Diels-Alder adduct wherein the dienophile is anitroso compound is represented by the formula:

wherein R can be hydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl,aryl, aralkyl, chloroalkyl, fluoroalkyl, substituted aryl having asubstituent selected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H, —SO₃H,trialkylsilyl and acyl; wherein the acyl is represented by the formula:R⁸CO— wherein R⁸ can be hydrogen, alkyl of 1-12 carbon atoms, aryl,substituted aryl, aralkyl and fluoroalkyl.

Other acylnitroso compounds of general formula R—CO—N═O are veryattractive and judged by its adduct with anthracene derivative can beconverted back to pentacene at moderate temperatures. An example wouldbe the reaction of pentacene with N-oxyacetamide (R=CH₃—) which can begenerated from acetylhydroxamic acid and reacted with pentacene in thepresence of methyl rhenium trioxide to give desired adduct as shownbellow.

In the above reaction R— can be chosen from alkyl groups of having oneto twelve carbon atoms, halogenated alkyl groups like CF₃—(CF₂)_(n)—where n is from zero to 10. R could be also an aryl group like phenyl orsubstituted phenyl with substituents like one or more halogens (Cl, Fand Br), nitro group, carboxylic acid or esters, amines or amides,phosphonic acid or ester, trialkyl or trialkoxysilane.

The adducts in which nitrogen is connected to an acyl (RCO) group couldfurther be hydrolyzed to corresponding —NH group by treatment with baseas shown in the following reaction.

Films of these adducts are prepared from solution by differenttechniques, e.g., spin-coating, casting, doctor blading, etc. Once filmsof these adducts on substrates are formed, they can easily be convertedback to pentacene by heating the substrate on a hot plate or in an ovenat modest temperatures. Any residual compounds other than pentaceneformed during retro Diels-Alder reaction can be removed by dipping thesubstrate solvents like alcohols, ethers, ketones and the like, to getpure pentacene films.

In the examples listed above the diene which was employed in Diels-Alderreactions has been pentacene, but other members of polyacenes liketetracene, hexacene and heptacene (structure I, n=2, 4 and 5respectively) can also be used to make soluble derivatives with heterodienophiles.

Although in all the structures depicted so far, the dienophile hasattached to the middle ring of pentacene (or polyacene in general) it ispossible to have the dienophile react with other ring in polycyclicaromatic compounds like pentacene, as depicted in the followingstructure with R¹—X═Y—R² representing hetero dienophiles of thisinvention:

wherein each X and Y is independently selected from: N and CR⁷;

wherein R¹—X═ can be O, S, SO and SO₂; and

wherein each R¹, R² and R⁷ is independently selected from: hydrogen,alkyl of 1-12 carbon atoms, aryl, substituted aryl, aralkyl,alkoxycarbonyl, aryloxycarbonyl, acyl and a group R, wherein R can behydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl, aryl, aralkyl,chloroalkyl, fluoroalkyl and substituted aryl having a substituentselected from: —F, —Cl, —Br, —NO₂, —CO₂R, —PO₃H, —SO₃H, trialkylsilyland acyl; wherein the acyl is represented by the formula: R⁸CO— whereinR⁸ can be hydrogen, alkyl of 1-12 carbon atoms, aryl, substituted aryl,aralkyl and fluoroalkyl;

with the proviso that at least one of X and Y is a hetero atom selectedfrom: N, O and S.

In the cases where the small molecule organic semiconductor layer isproduced by at least a partial conversion of a precursor of the smallorganic molecule during the step of exposing the donor substrate toenergy the donor substrate has a predeposited thin precursor filmthereon. When the donor substrate, and optionally the energy absorbingfilm, are exposed to the energy, the resultant heat causes theconversion of the precursor to the small molecule organic semiconductorlayer and the thermal transfer of the small organic molecule onto theacceptor substrate.

In certain situations, some precursor will sublime and deposit onto theacceptor substrate without conversion to the small organic molecule. Inthese situations the acceptor substrate can be annealed after thethermal transfer at about the thermal decomposition temperature of theprecursor to convert any remaining precursor to the small organicmolecule.

It has also been shown that heating the acceptor substrate prior tothermal transfer improves the thermal transfer of the small organicmolecule onto the acceptor substrate. Heating is carried out at atemperature in the range from about 25° C. to about 100° C., preferablyfrom about 25° C. to about 75° C., depending on the particular smallmolecule. This heating can be used alone or in combination with theannealing discussed above.

The energy used to expose the donor substrate can be selected from anysufficient to cause the thermal transfer of the small organic moleculeand the conversion of any precursor used. Non-limiting examples ofsuitable energy from an energy source are infrared, ultraviolet,visible, thermal, electron beam, ion beam, x-ray beam, energy beam,pulsed energy, continuous wave (cw) energy, focused laser, pulsed laser,cw laser, thermal probe, resistive heating, a heated AFM probe, asoldering iron tip, or any combination thereof. A non-limiting exampleof resistive heating includes resistance losses due to the passage of alocal current pulse in contact with the donor substrate. The energysource can produce energy that exposes small portions of the donorsubstrate at a time to the energy. The energy source can optionallyproduce energy that floods the donor substrate with energy. A mostpreferred energy is a focused laser beam.

In the current invention the donor substrate may be moved relative tothe energy source and the acceptor substrate. Also, the energy may bemoved relative to the donor substrate and the acceptor substrate.Non-limiting examples of this movement include moving the energy sourceitself and scanning the energy relative to the substrates. Furthermore,the acceptor substrate may be moved relative to the energy source andthe donor substrate. All of these movements can be employed singly or incombination. Means for and methods of implementing these movements arewell known and one of ordinary skill in the art should be capable ofconfiguring.

FIG. 4 shows a simple system of the present invention having means formoving the acceptor substrate 400 and means for moving the donorsubstrate 405 relative to each other and the energy 215 from energysource 210. FIG. 4 shows an energy absorbing donor substrate system withan energy absorbing substrate 205 and small molecule organicsemiconductor layer 200 for example purposes only, and is not meant tolimit the application of the means of movement.

FIG. 5 shows a simple system of the present invention having means formoving the energy source 500 relative to the donor substrate 300 (here,a transparent substrate by example) and acceptor substrate 100. Byemploying any of the means for movement illustrated in FIGS. 4 and 5,alone or in combination, it is possible to create patterns of the smallorganic molecule on the surface of the acceptor substrate 100 asindicated by the patterned small molecule organic semiconductor layer105 in FIG. 1.

An alternative embodiment can further include, possibly eliminating theneed to move the substrates and the energy, a mask placed between thedonor substrate and the acceptor substrate. FIG. 6 a shows a crosssectional view of a simple system of the present invention where a mask620 with a solid portion 630 and an open portion 625. The open portion625 corresponds to the desired dimensions of the patterned smallmolecule organic semiconductor layer 105 to be produced on the acceptorsubstrate 100. Flood energy 615 is incident on the donor substrate 300(here, an energy transparent substrate by example). As the generatedheat is transferred from the entire illuminated region of energyabsorbing film 305, the small molecule organic semiconductor layer 200sublimes. The solid portion 630 of the mask 625 acts as a physical blockto the subliming and depositing small molecule and allows patterning onthe acceptor substrate 100 of the patterned small molecule organicsemiconductor layer 105.

FIG. 6 b shows a top view of a mask 620 with solid portion 630 and openportion 625. Here, the open portion 625 is dimensioned as an “H”pattern, however, any desired pattern dimensions can be utilized. Theacceptor substrate 100 is visible below the mask.

In another embodiment the donor substrate is a disk mounted on arotatable axis. The donor substrate can be rotated around the axis andthe energy incident at a point on the donor substrate. As the donorsubstrate rotates, the energy causes the heating, and thus the thermaltransfer, of a new portion of the small molecule organic semiconductorlayer. By displacing the axis relative to the energy and/or by movingthe energy relative to the disk, the entire portion of the smallmolecule organic semiconductor layer can be utilized. The acceptorsubstrate may also be moved.

FIG. 7 shows a cross sectional view of an example of the disk mounted ona rotatable axis embodiment. Here, an energy transparent substrate 300with an energy absorbing film 305 is used by example. The energytransparent substrate 300 is in the form of a rotatable disk 700attached at an axis 710 to a means to rotate the disk 705. Energy 215from energy source 210 is incident on the disk such to cause the heatingof the small molecule organic semiconductor layer 200 pre-depositedthereon and the thermal transfer of the small organic molecule onto theacceptor substrate 100. FIG. 7 shows a patterned small molecule organicsemiconductor layer 225 corresponding to the width of the energy 215. Byrotating the disk 700 a different region of the small molecule organicsemiconductor layer 200 would be affected by the energy 215 and thussublimed and deposited on the acceptor substrate 100. Means fordisplacing the disk axis 715 can be utilized to move the disk 700 inrelation to the energy 215 and acceptor substrate 100, for example tobring energy 215 incident upon a different radius of disk 700 and thusutilize the full area of the small molecule organic semiconductor 200.Alternately or in combination with 715, means for moving the energy 500can be utilized. Means for moving the acceptor substrate 400 can also beutilized singly or in combination with the movement of the othercomponents.

The method and system of the present invention can be practiced in avacuum or under regular atmospheric conditions. Under regularatmospheric conditions the donor substrate and acceptor substrate can bein contact or separated slightly, typically by less than 1 cm. It hasalso been unexpectedly found that the thermal transfer is improved whenthe small molecule organic semiconductor layer on the donor substrateand the acceptor substrate are in intimate contact. Intimate contactrefers to having a contact area which is substantially free ofatmospheric gases. In certain situations it is necessary to applypressure to achieve this intimate contact. Non-limiting examples ofmethods of applying pressure include a planar pressure device, anilluminated doctor blade, and a waveguide tip.

The system, method, and product of the present invention achieve thermaltransfer of small molecule organic semiconductor or semiconducting filmfrom one surface to a second surface. This type of transfer makes itpossible, for example, to ‘print’ channels onto field effect transistorstructures or to deposit regions of small molecule organicsemiconducting films for organic light emitting diodes.

To achieve these examples of the present invention, components to anelectronic structure can be added to the substrate. FIG. 8 shows anacceptor substrate 100 having thereon a component to an electronicstructure 800 with a patterned small molecule organic semiconductorlayer 225. In a preferred embodiment, the component to an electronicstructure can comprise source, drain, and gate elements of a fieldeffect transistor. In this preferred embodiment, the patterned smallmolecule organic semiconductor layer forms a channel of the field effecttransistor. FIG. 9 shows one simple example of a field effect transistoron an acceptor substrate 100 with gate 905, gate oxide 910, drain 915,and source 920 elements. The patterned small molecule organicsemiconductor layer 105 forms the channel of the field effecttransistor. In another preferred embodiment, the patterned smallmolecule organic semiconductor layer forms an active layer of an organiclight emitting diode. In another preferred embodiment, the components toan electronic structure are components of a photodiode.

In yet another embodiment, the donor substrate is a ribbon. The ribboncan be rigid or flexible depending on the application. When the donorsubstrate is a ribbon, it is possible for the ribbon to be part of areel-to-reel apparatus. FIG. 10 shows a ribbon 1000 (here for examplepurposes only made of a flexible, energy transparent material) with anenergy absorbing film 305 and small molecule organic semiconductor layer200 deposited along the entire length of the ribbon 1000. A preferredreel-to-reel apparatus has a reel 1010 around which is wound the ribbonand another reel 1015 onto which the ribbon is wound as the ribbonpasses through an area where it is exposed to the energy 215 from energysource 210 and the small molecule organic semiconductor layer 200sublimes and is deposited onto the acceptor substrate 100. As the ribbon1000 is wound around spindle 1020 of reel 1015 by a means configurableby one of ordinary skill in the art, a patterned small molecule organicsemiconductor layer 225 (here, for example purposes, dimensionedcorresponding to the radius of the incident energy 215). As with otherembodiments of the invention, it is possible to have means for movingthe energy 500 and means for moving the acceptor substrate 200. Oneresult of this relative movement is the production any number ofdifferent patterns of the small organic molecule on the acceptorsubstrate.

In still yet another embodiment, the donor substrate is in the shape ofa hollow cylindrical roller having an inner and an outer surface. Theouter surface is where the small molecule organic semiconductor layerresides. As is possible in all embodiments of the invention, when thehollow cylindrical roller is made of an energy transparent material,there can be an energy absorbing film between the outer surface of thehollow cylindrical roller and the small molecule organic semiconductorlayer. The basic structure of the novel apparatus consists of a hollowcylinder or drum free to rotate by computer control, with the cylinderpreferably made from a material that transmits light in the visible, forexample glass or plastic. In one embodiment, the outer periphery of thecylinder has a thin coating of an optically absorbing material with thesmall molecule organic semiconductor layer disposed thereon. Again, thesmall organic molecule may be pentacene or one of its precursors butagain not limited to that particular small molecule organicsemiconductor.

The energy source can be at a point within the hollow cylindricalroller. The energy source within the hollow cylindrical roller can beone or more laser diodes. Typically, the point is along the axis of thehollow cylindrical roller such that the energy from the energy source isdirected at the inner surface of the hollow cylindrical roller in thedirection of the acceptor substrate. Alternatively, the energy sourcecan be along a line, preferably parallel to the axis of the cylinder.This line can be close to the periphery of the cylinder. A means formoving the axis of the cylinder from the true axis of the cylinder canalso be employed to bring the energy source to different positionsrelative to the periphery of the cylinder. It is possible for thisenergy source to be moveable from one point to another within the hollowcylindrical roller, usually, but not restricted to, along the axis. Theenergy source can be computer controlled with respect to its on-offmodes of operation and location. Typically the on-off modes of operationare controlled with respect to time and the relative position of thehollow cylindrical roller and the energy source. An example of theplacement of the energy source is a single laser diode that can be movedalong the mounting axis and the roller moved stepwise after the laserhas traversed the entire length of the roller axis with the laser pulsedat designated positions to bring about thermal transfer.

The roller can be rolled in relation to the acceptor substrate. Anon-limiting example of a suitable acceptor substrate is a flat sheet,preferably a plastic sheet placed on a hard, non-compliant surfacewherein the hollow cylindrical roller is made to roll over the plasticsheet and the energy causes the thermal transfer of the small organicmolecule from the outside of the hollow cylindrical roller to theacceptor substrate. As mentioned above, the thermal transfer is improvedwhen the small molecule organic semiconductor layer and the acceptorsubstrate are in intimate contact. Often this intimate contact isachieved through the application of pressure so that the small moleculeorganic semiconductor layer and the acceptor substrate have a contactarea which is substantially free of atmospheric gases. A thermaltransfer of the organic material is made from the cylinder (donor) ontothe acceptor substrate as has been previously shown in a simplerembodiment by experimentation.

The energy absorbing film and the small molecule organic semiconductorlayer can be applied to the hollow cylindrical roller by any well knownmethod. Examples of these methods include sputtering, evaporating,spraying, dipping, spinning, and combinations thereof.

FIG. 11 a shows a cross sectional view of an example of the hollowcylindrical roller embodiment. Here, hollow cylindrical roller 1100 hasan outer material that is energy transparent with an inner surface 1105and an outer surface 1110. An energy absorbing film 305 has beendisposed on the outer surface 1110 and a small molecule organicsemiconductor layer 200 has been disposed thereon. Energy 215 fromenergy source 210 situated at a point 1120 within the hollow cylindricalroller is incident on the inner surface 1105 in the direction of theacceptor substrate 100 which is to receive the thermal transfer of thesmall organic molecule. FIG. 11 a further shows the optional means forapplying pressure 1115. FIG. 11 b shows a cut away view of a hollowcylindrical roller 1100 with the energy source 210 positioned at a pointalong the axis 1120 of the hollow cylindrical roller. Means fordisplacing 1125 the axis from true center is shown and the energy source210 is movable along the axis 1120. Energy 215 is incident on the innersurface 1105 of the hollow cylindrical roller. It is possible for thehollow cylindrical roller to be made of an energy absorbing material(not shown) and to have the small molecule organic semiconductor layerdirectly thereon.

In another embodiment, the energy source is disposed at a point within ahollow cylindrical roller having an inner and an outer surface. Here,the donor substrate is a first rigid or flexible material sheet havingthe small molecule organic semiconductor layer thereon. The acceptorsubstrate is a second rigid or flexible material sheet. The materialsheets are passed simultaneously between the hollow cylindrical rollersand a second roller which are in contact with one another along theirlongitudinal axes such to permit the thermal transfer of the smallorganic molecule from the first material sheet to the second materialsheet.

One or both of the two rollers may be slightly compliant, therebyallowing more than just line contact along the axis of the roller. Thisallows thermal transfer of material over small linear distances in adirection that is perpendicular to the axis of the roller alsocontrolled in part by the shape of the energy. The apparatus can be madeto allow for a constant feed-through of both materials to provide largescale production.

It is possible that the first material sheet and the small moleculeorganic semiconductor layer have an energy absorbing film interposedbetween them. Often when the first material sheet is an energytransparent material, this energy absorbing film is necessary to absorbthe energy. The material sheets can be made of any suitable material. Ina preferred embodiment the material sheets are made of a flexibleplastic. Non-limiting examples of flexible plastic include MYLAR™ andKAPTON™.

It is also possible, however, for the first material sheet to be anenergy absorbing material.

The energy source within the hollow cylindrical roller can be one ormore laser diodes. Typically, the energy source is along the axis of thehollow cylindrical roller such that the energy from the energy source isdirected at the inner surface of the hollow cylindrical roller in thedirection of the acceptor substrate. It is possible for this energysource to be moveable from one point to another within the hollowcylindrical roller, usually, but not restricted to, along the axis. Theenergy source can be computer controlled with respect to its on-offmodes of operation. Typically this the on-off modes of operation arecontrolled with respect to time and the relative position of the hollowcylindrical roller.

As mentioned above, the thermal transfer is improved when the smallmolecule organic semiconductor layer and the acceptor substrate are inintimate contact. Often this intimate contact is achieved through theapplication of pressure so that the small molecule organic semiconductorlayer and the acceptor substrate have a contact area which issubstantially free of atmospheric gases. For example, the two rollerscan be brought into intimate contact at a predetermined compression setby adjustable springs on at least one of the rollers or by any othermeans capable of producing such intimate contact.

FIG. 12 shows a cross sectional view of an example of the foregoingembodiment. A first material sheet 825 (here made of a energytransparent material) with an energy absorbing film 305 and a smallmolecule organic semiconductor layer 200 and a second material sheet1230 are simultaneously passed between a hollow cylindrical roller 1200and a second roller 1235. Energy 215 from energy source 210 along theaxis 1220 of the hollow cylindrical roller 1200 is incident on the innersurface 1205 of the hollow cylindrical roller 1200. The energy passesthrough the hollow cylindrical roller and the energy transparent firstmaterial sheet 825 thus being absorbed by the energy absorbing film 305causing heat to be transferred to the small molecule organicsemiconductor layer 200. This heat causes the thermal transfer of smallmolecule to the second material sheet 1230. FIG. 12 shows optional means1215 and 1240 for applying pressure.

To those skilled in the art, it is clear that many possible variationsof these configurations are possible.

In addition to being directed to the method for preparing the substratehaving the patterned small molecule organic semiconductor layer thereon,this invention is directed to a substrate with a patterned smallmolecule organic semiconductor layer comprising a small organic moleculethermally transferred by exposing a donor substrate having thereon asmall organic molecule organic semiconductor layer to energy.

The invention is still further directed to a system for producing asubstrate having thereon the patterned small molecule organicsemiconductor layer. Features of the production of a substrate havingthereon the patterned small molecule organic semiconductor have beendiscussed in detail in relation to the method herein above. The systemincludes a donor substrate with a small molecule organic semiconductorlayer thereon; an acceptor substrate positioned to receive the patternedsmall molecule organic semiconductor layer upon exposing the donorsubstrate to energy; and an energy source to produce the energy to causethe thermal transfer of a small organic molecule onto the acceptorsubstrate.

The features of the following embodiments of the system, and otherembodiments of the system have been described in detail in relation tothe method herein above.

The system of the present invention can also include an energy absorbingfilm interposed between the donor substrate and the small moleculeorganic semiconductor layer to absorb the energy and cause thermaltransfer of the small organic molecule.

As discussed above in relation to the method the small molecule organicsemiconductor layer can be produced by an at least partial conversion ofa precursor of the small organic molecule during the exposing of thedonor substrate.

The system can have a heating source to anneal the acceptor substrateafter the thermal transfer of the patterned small molecule organicsemiconductor layer on the acceptor substrate. The annealing can beperformed at about the thermal decomposition temperature of theprecursor to convert any remaining precursor to small molecule.

The system can have means for relatively moving the donor substrate,acceptor substrate, energy source, or a combination thereof.

The system can have a mask, wherein the mask is interposed between thedonor substrate and the acceptor substrate.

The system can have a donor substrate that is a rigid or flexibleribbon. The ribbon can be part of a reel to reel apparatus.

The system can have a donor substrate that is a disk mounted on arotatable axis.

The system can include components of an electronic structure asdescribed in detail relative to the method of the invention.

The system can have a donor substrate that is in the shape of a hollowcylindrical roller having an inner and an outer surface, wherein theouter surface has thereon a small molecule organic semiconductor layer.

The system can have an energy source that is disposed at a point withina hollow cylindrical roller having an inner and an outer surface;wherein the donor substrate is an optically transparent first rigid orflexible material sheet having an energy absorbing film interposedbetween the donor substrate and a small molecule semiconductor layer. Anacceptor substrate is a second rigid or flexible material sheet. Thefirst and second material sheets are passed simultaneously between thehollow cylindrical roller and a second roller. The rollers can be incontact with one another along their longitudinal axes to permit thethermal transfer of the small organic molecule from the first materialsheet to the second material sheet.

The present invention has been described with particular reference tothe preferred embodiments. It should be understood that the foregoingdescriptions and examples are only illustrative of the invention.Various alternatives and modifications thereof can be devised by thoseskilled in the art without departing from the spirit and scope of thepresent invention. Accordingly, the present invention is intended toembrace all such alternatives, modifications, and variations that fallwithin the scope of the appended claims.

1. A method of preparing a substrate having thereon a patterned smallmolecule organic semiconductor layer, said method comprising: exposing adonor substrate having thereon a small molecule organic semiconductorlayer to energy produced from an energy source to cause the thermaltransfer of a small organic molecule onto an acceptor substrate toproduce a substrate having thereon said patterned small molecule organicsemiconductor; wherein said small molecule organic semiconductor layeris produced by at least a partial conversion of a precursor of saidsmall organic molecule during the step of exposing said donor substrate.2. The method of claim 1, wherein said donor substrate and said smallmolecule organic semiconductor layer have an energy absorbing filminterposed therebetween.
 3. The method of claim 1, wherein said donorsubstrate is an energy absorbing material or an energy transparentmaterial.
 4. The method of claim 1, wherein said patterned smallmolecule organic semiconductor layer comprises a polycyclic aromaticcompound, said polycyclic aromatic compound represented generally by theformula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, a group wherein R³ and R⁴ together form one or more fused benzorings and a group wherein R⁵ and R⁶ together form one or more fusedbenzo rings; and wherein n is at least
 1. 5. The method of claim 4,wherein said polycyclic aromatic compound is pentacene.
 6. The method ofclaim 1, wherein said precursor is a precursor to a polycyclic aromaticcompound; wherein said precursor to a polycyclic aromatic compound is aDiels-Alder adduct of a polycyclic aromatic compound with a dienophile,wherein said polycyclic aromatic compound is selected from the groupconsisting of: oligothiophene, perylene, benzo[ghi]perylene, coroneneand polyacene; and wherein said dienophile is represented by theformula:  R¹—X═Y—R² wherein each X and Y is independently selected fromthe group consisting of: N and CR⁷; wherein R¹—X═ is selected from thegroup consisting of: O, S, SO and SO₂; and wherein each R¹, R² and R⁷ isindependently selected from the group consisting of: hydrogen, alkyl of1-12 carbon atoms, aryl, substituted aryl, aralkyl, alkoxycarbonyl,aryloxycarbonyl, acyl and a group R, wherein R is selected from thegroup consisting of: hydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl,aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted aryl having asubstituent selected from the group consisting of: —F, —Cl, —Br, —NO₂,—CO₂R, —PO₃H, —SO₃H, trialkylsilyl and acyl; wherein said acyl isrepresented by the formula: R⁸CO— wherein R⁸ is selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, aralkyl and fluoroalkyl; with the proviso that at least one of Xand Y is a hetero atom selected from the group consisting of: N, O andS.
 7. The method of claim 1, wherein said energy is selected from thegroup consisting of: infrared, ultraviolet, visible, thermal, electronbeam, ion beam, energy beam, pulsed energy, continuous wave (cw) energy,focused laser, pulsed laser, cw laser, thermal probe, resistive heating,a heated AFM probe, a soldering iron tip, and combinations thereof. 8.The method of claim 1, wherein said acceptor substrate is heated.
 9. Themethod of claim 8, wherein said heating is carried out in a mannerselected from the group consisting of: (a) prior to said thermaltransfer of said patterned small molecule organic semiconductor layer,wherein said heating is carried out at a temperature in the range fromabout 25° C. to about 100° C., depending on the particular said smallorganic molecule; (b) after said deposition of said patterned smallmolecule organic layer on said acceptor substrate, wherein said heatingis at about the thermal decomposition temperature of said precursor toconvert any remaining precursor to said small organic molecule. (c) anycombination of (a)-(b) above.
 10. The method of claim 1, furthercomprising a step selected from the group consisting of: (a) moving saiddonor substrate relative to said energy source and said acceptorsubstrate; (b) moving said energy relative to said donor substrate andsaid acceptor substrate; p1 (c) moving said acceptor substrate relativeto said energy source and said donor substrate; and (d) any combinationof (a)-(d) above.
 11. The method of claim 1, further comprising:inserting a mask between said donor substrate and said acceptorsubstrate.
 12. The method of claim 1, wherein said donor substrate is adisk mounted on a rotatable axis.
 13. The method of claim 1, whereinsaid energy is a focused laser.
 14. The method of claim 13, wherein saidpatterned small molecule organic semiconductor layer is a channel of afield effect transistor.
 15. The method of claim 13, wherein said smallmolecule organic semiconductor layer forms an active layer of an organiclight emitting diode.
 16. The method of claim 1, wherein said donorsubstrate is a rigid or flexible ribbon.
 17. The method of claim 16,wherein said ribbon is part of a reel to reel apparatus.
 18. The methodof claim 1, wherein said donor substrate is in the shape of a hollowcylindrical roller having an inner and an outer surface, said outersurface having thereon said small molecule organic semiconductor layer.19. The method of claim 18, wherein said energy source is at a pointwithin said hollow cylindrical roller.
 20. The method of claim 19,wherein said point within said hollow cylindrical roller is along theaxis of said hollow cylindrical roller such that said energy from saidenergy source is directed at said inner surface of said hollowcylindrical roller in the direction of said acceptor substrate.
 21. Themethod of claim 19, wherein said energy source is computer controlledwith respect to on-off modes of operation.
 22. The method of claim 1,wherein said energy source is disposed at a point within a hollowcylindrical roller having an inner and an outer surface; wherein saiddonor substrate is a first rigid or flexible material sheet having saidsmall molecule organic semiconductor layer thereon; wherein saidacceptor substrate is a second rigid or flexible material sheet, whereinsaid first and said second material sheets are passed simultaneouslybetween said hollow cylindrical roller and a second roller, said rollersbeing in contact with one another along their longitudinal axes topermit said sublimation and said deposition of said small organicmolecule from said first material sheet to said second material sheet.23. A method of preparing a substrate having thereon a patterned smallmolecule organic semiconductor layer, said method comprising: exposing adonor substrate having thereon a small molecule organic semiconductorlayer to energy produced from an energy source to cause the thermaltransfer of a small organic molecule onto an acceptor substrate toproduce a substrate having thereon said patterned small molecule organicsemiconductor layer; wherein said patterned small molecule organicsemiconductor layer comprises a polycyclic aromatic compound, saidpolycyclic aromatic compound represented generally by the formula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, a group wherein R³ and R⁴ together form one or more fused benzorings and a group wherein R⁵ and R⁶ together form one or more fusedbenzo rings; and wherein n is at least
 1. 24. The method of claim 23,wherein said polycyclic aromatic compound is pentacene.
 25. The methodof claim 23, wherein said energy is selected from the group consistingof: infrared, ultraviolet, visible, thermal, electron beam, ion beam,energy beam, pulsed energy, continuous wave (cw) energy, focused laser,pulsed laser, cw laser, thermal probe, resistive heating, a heated AFMprobe, a soldering iron tip, and combinations thereof.
 26. The method ofclaim 23, wherein said acceptor substrate is heated.
 27. The method ofclaim 26, wherein said heating is carried out in a manner selected fromthe group consisting of: (a) prior to said thermal transfer of saidpatterned small molecule organic semiconductor layer, wherein saidheating is carried out at a temperature in the range from about 25° C.to about 100° C., depending on the particular said small organicmolecule; (b) after said deposition of said patterned small moleculeorganic layer on said acceptor substrate, wherein said heating is atabout the thermal decomposition temperature of said precursor to convertany remaining precursor to said small organic molecule. (c) anycombination of (a)-(b) above.
 28. The method of claim 23, furthercomprising a step selected from the group consisting of: (a) moving saiddonor substrate relative to said energy source and said acceptorsubstrate; (b) moving said energy relative to said donor substrate andsaid acceptor substrate; (c) moving said acceptor substrate relative tosaid energy source and said donor substrate; and (d) any combination of(a)-(d) above.
 29. The method of claim 23, further comprising: insertinga mask between said donor substrate and said acceptor substrate.
 30. Themethod of claim 23, wherein said donor substrate is a disk mounted on arotatable axis.
 31. A method of preparing a substrate having thereon apatterned small molecule organic semiconductor layer, said methodcomprising: exposing a donor substrate having thereon a small moleculeorganic semiconductor layer to energy produced from an energy source tocause the thermal transfer of a small organic molecule onto an acceptorsubstrate to produce a substrate having thereon said pattered smallmolecule organic semiconductor layer; wherein said acceptor substrate isheated.
 32. The method of claim 31, wherein said heating is carried outin a manner selected from the group consisting of: (a) prior to saidthermal transfer of said patterned small molecule organic semiconductorlayer, wherein said heating is carried out at a temperature in the rangefrom about 25° C. to about 100° C., depending on the particular saidsmall organic molecule; (b) after said deposition of said patternedsmall molecule organic layer on said acceptor substrate, wherein saidheating is at about the thermal decomposition temperature of saidprecursor to convert any remaining precursor to said small organicmolecule. (c) any combination of (a)-(b) above.
 33. The method of claim31, further comprising a step selected from the group consisting of: (a)moving said donor substrate relative to said energy source and saidacceptor substrate; (b) moving said energy relative to said donorsubstrate and said acceptor substrate; (c) moving said acceptorsubstrate relative to said energy source and said donor substrate; and(d) any combination of (a)-(d) above.
 34. The method of claim 31,further comprising: inserting a mask between said donor substrate andsaid acceptor substrate.
 35. The method of claim 31, wherein said donorsubstrate is a disk mounted on a rotatable axis.
 36. A method ofpreparing a substrate having thereon a patterned small molecule organicsemiconductor layer, said method comprising: exposing a donor substratehaving thereon a small molecule organic semiconductor layer to energyproduced from an energy source to cause the thermal transfer of a smallorganic molecule onto an acceptor substrate to produce a substratehaving thereon said patterned small molecule organic semiconductorlayer; wherein said donor substrate is a disk mounted on a rotatableaxis.
 37. The method of claim 36, wherein said donor substrate and saidsmall molecule organic semiconductor layer have an energy absorbing filminterposed therebetween.
 38. The method of claim 36, wherein said donorsubstrate is an energy absorbing material or an energy transparentmaterial.
 39. The method of claim 36, wherein said patterned smallmolecule organic semiconductor layer comprises a polycyclic aromaticcompound, said polycyclic aromatic compound represented generally by theformula:

wherein each R³, R⁴, R⁵ and R⁶ is independently selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, a group wherein R³ and R⁴ together form one or more fused benzorings and a group wherein R⁵ and R⁶ together form one or more fusedbenzo rings; and wherein n is at least
 1. 40. The method of claim 39,wherein said polycyclic aromatic compound is pentacene.
 41. The methodof claim 36, wherein said small molecule organic semiconductor layer isproduced by at least a partial conversion of a precursor of said smallorganic molecule during the step of exposing said donor substrate. 42.The method of claim 41, wherein said precursor is a precursor to apolycyclic aromatic compound; wherein said precursor to a polycyclicaromatic compound is a Diels-Alder adduct of a polycyclic aromaticcompound with a dienophile, wherein said polycyclic aromatic compound isselected from the group consisting of: oligothiophene, perylene, benzoperylene, coronene and polyacene; and wherein said dienophile isrepresented by the formula:R¹—X═Y—R² wherein each X and Y is independently selected from the groupconsisting of: N and CR⁷; wherein R¹—X═ is selected from the groupconsisting of: O, S, SO and SO₂; and wherein each R¹, R² and R⁷ isindependently selected from the group consisting of: hydrogen, alkyl of1-12 carbon atoms, aryl, substituted aryl, aralkyl, alkoxycarbonyl,aryloxycarbonyl, acyl and a group R, wherein R is selected from thegroup consisting of: hydrogen, alkyl of 1-12 carbon atoms, alkoxy, acyl,aryl, aralkyl, chloroalkyl, fluoroalkyl and substituted aryl having asubstituent selected from the group consisting of: —F, —Cl, —Br, —NO₂,—CO₂R, —PO₃H, —SO₃H, trialkylsilyl and acyl; wherein said acyl isrepresented by the formula: R⁸CO— wherein R⁸ is selected from the groupconsisting of: hydrogen, alkyl of 1-12 carbon atoms, aryl, substitutedaryl, aralkyl and fluoroalkyl; with the proviso that at least one of Xand Y is a hetero atom selected from the group consisting of: N, O andS.
 43. The method of claim 36, wherein said energy is selected from thegroup consisting of: infrared, ultraviolet, visible, thermal, electronbeam, ion beam, energy beam, pulsed energy, continuous wave (cw) energy,focused laser, pulsed laser, cw laser, thermal probe, resistive heating,a heated AFM probe, a soldering iron tip, and combinations thereof.